EP2936219A1 - Réseau de nanostructures antireflet et procédé - Google Patents

Réseau de nanostructures antireflet et procédé

Info

Publication number
EP2936219A1
EP2936219A1 EP14710747.8A EP14710747A EP2936219A1 EP 2936219 A1 EP2936219 A1 EP 2936219A1 EP 14710747 A EP14710747 A EP 14710747A EP 2936219 A1 EP2936219 A1 EP 2936219A1
Authority
EP
European Patent Office
Prior art keywords
nanostructures
array
nanostructure
reflection
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP14710747.8A
Other languages
German (de)
English (en)
Inventor
Michael F. STOIA
Authi A. NARAYANAN
Stephen K. WILCKEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Boeing Co
Original Assignee
Boeing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Boeing Co filed Critical Boeing Co
Publication of EP2936219A1 publication Critical patent/EP2936219A1/fr
Pending legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures

Definitions

  • This application relates to anti-reflection and, more particularly, to anti-reflection nanostructure arrays.
  • Optical reflections are undesirable in many fields, such photovoltaics (e.g., solar cells), lighting (e.g., light emitting diodes), displays (e.g., computer displays and televisions), windows (e.g., windshields), sensors, detectors, gun sights, binoculars, spectacles and sunglasses.
  • photovoltaics e.g., solar cells
  • lighting e.g., light emitting diodes
  • displays e.g., computer displays and televisions
  • windows e.g., windshields
  • sensors detectors, gun sights, binoculars, spectacles and sunglasses.
  • a substantial portion e.g., 30 percent or more
  • the sunlight applied to a typical silicon solar cell may be reflected at the surface of the solar cell, thereby significantly reducing the amount of light absorbed by the solar cell and, hence, the amount of electrical energy that may be generated by the solar cell.
  • the optical reflection occurs at the air-to-solar cell interface because air has an index of refraction that is substantially less than the index of refraction of silicon.
  • anti-reflection coatings have been developed in an attempt to reduce optical reflections. More recently, anti-reflection nanostructures have been developed to reduce optical reflections. Both traditional index-matched coatings and modern anti- reflection nanostructures reduce optical reflections because the apparent index of refraction of the anti-reflection layer is less than, and transitions to, the index of refraction of the underlying substrate. Nonetheless, additional improvement in optical reflection reduction is desired.
  • the disclosed anti-reflection nanostructure assembly may include a substrate and an array of nanostructures on the substrate, wherein the array of nanostructures is substantially free of interstitial gaps such that the apparent index of refraction of the array, in a direction perpendicular to said surface, varies smoothly.
  • the disclosed anti-reflection nanostructure assembly may include a substrate and an array of nanostructures, wherein each nanostructure of the array includes a proximal end and a distal end, and is tapered from the proximal end to the distal end, and wherein the proximal end of each nanostructure of the array is contiguous with the proximal ends of adjacent nanostructures of the array to form a contiguous layer on the substrate.
  • the disclosed method for reducing reflectance at an interface may include the steps of (1 ) providing a substrate and (2) forming an array of
  • each nanostructure includes a proximal end and a distal end, and is tapered from the proximal end to the distal end, and wherein the proximal end of each nanostructure is contiguous with the proximal ends of adjacent nanostructures to form a contiguous layer on the substrate.
  • Fig. 1 A is a top plan view of a prior art anti-reflection nanostructure assembly, which includes a nanostructure array on a substrate;
  • Fig. 1 B is a side cross-sectional view of the anti-reflection nanostructure assembly of Fig. 1A;
  • Fig. 2A is a top plan view of an aspect of the disclosed anti-reflection
  • Fig. 2B is a side cross-sectional view of the anti-reflection nanostructure assembly of Fig. 2A;
  • Fig. 3 is a graphical representation of the apparent index of refraction of the anti- reflection nanostructure array of Figs. 1 A and 1 B compared to the apparent index of refraction of the anti-reflection nanostructure array of Figs. 2A and 2B;
  • Fig. 4 is a side cross-sectional view of one particular aspect of the disclosed anti- reflection nanostructure assembly;
  • Figs. 5A, 5B and 5C are side elevational, top plan and perspective views, respectively, of an aspect of the disclosed nanostructure array having a square packing configuration
  • Figs. 6A, 6B and 6C are side elevational, top plan and perspective views, respectively, of an aspect of the disclosed nanostructure array having a hexagonal packing configuration
  • Fig. 7A is a top plan view of a periodic nanostructure array in accordance with one aspect of the present disclosure
  • Fig. 7B is a top plan view of a non-periodic nanostructure array with 20 percent position variation in accordance with another aspect of the present disclosure
  • Fig. 7C is a top plan view of a non-periodic nanostructure array with 50 percent position variation in accordance with yet another aspect of the present disclosure
  • Fig. 8 is a graphical representation of reflectance versus wavelength for anti- reflection nanostructure assemblies both with and without interstitial gaps;
  • Fig. 9 is a schematic side elevational view of one aspect of the disclosed method for manufacturing an anti-reflection nanostructure assembly.
  • Fig. 10 is a flow chart depicting one aspect of the disclosed method for reducing reflectance at an air-to-substrate interface. DETAI L ED DESCR I PTI ON
  • a conventional anti-reflection nanostructure assembly As shown in Figs. 1 A and 1 B, a conventional anti-reflection nanostructure assembly, generally designated 2, includes a substrate 4 (e.g., ethylene
  • the nanostructure array 6 defines interstitial gaps 8 between adjacent nanostructures of the nanostructure array 6, thereby exposing portions of the underlying substrate 4.
  • the disclosed anti-reflection nanostructure assembly may include a substrate 12 (e.g., ETFE) and a nanostructure array 14 on the substrate 12.
  • the nanostructure array 14 may be configured to, among other things, substantially (if not completely) eliminate interstitial gaps and, thus, substantially (if not completely) eliminate exposed substrate 12.
  • interstitial gaps between the nanostructures of a conventional anti-reflection nanostructure array expose underlying substrate, which causes a local discontinuity in the apparent index of refraction when
  • the discontinuity may lead to reduced anti-reflection performance of the nanostructure array.
  • Reducing or eliminating interstitial gaps may reduce or eliminate exposed substrate, which may correspondingly reduce or eliminate local discontinuities, thereby significantly improving anti-reflection performance.
  • one aspect of the disclosed anti-reflection nanostructure assembly may include a substrate 52 and a plurality of nanostructures 54.
  • the substrate 52 may include a first major surface 56 and a second major surface 58.
  • the nanostructures 54 may be arranged as an array 60 on the first major surface 56 of the substrate 52.
  • the substrate 52 may be formed from various materials. Those skilled in the art will appreciate that substrate material selection may depend on application.
  • the substrate 52 may be formed from optical materials, such as optical materials that are transparent (or at least partially transparent) to visible light, infrared light and/or ultraviolet light.
  • the substrate 52 may be formed from a polymer material.
  • Examples of polymer materials suitable for use as the substrate 52 include, but are not limited to, ethylene tetrafluoroethylene (“ETFE”), fluorinated ethylene propylene (“FEP”), and polycarbonate.
  • the substrate 52 may be formed from glass, such as a silicate glass.
  • the substrate 52 may be formed from a semiconductor material. Examples of semiconductor materials suitable for use as the substrate 52 include, but are not limited to, silicon and gallium arsenide.
  • the substrate 52 may be configured in various ways.
  • the substrate 52 may be configured as a film, a wafer, a panel, a lens or the like.
  • substrate configuration may depend on application and the type of substrate materials being used, among other factors.
  • the nanostructures 54 may also be formed from various materials. Those skilled in the art will appreciate that nanostructure material selection may be dictated by, among other things, the type of substrate material being used, the method used to form the nanostructures 54, and the end application. In one realization, the nanostructures 54 may be formed from the same material as the substrate 52. As one specific, non-limiting example, both the nanostructures 54 and the substrate 52 may be formed from an optical polymer, such as ETFE.
  • the nanostructures 54 may be integral with the substrate 52 (the first resistor 52 ).
  • nanostructures 54 and substrate 52 may be formed as a single monolithic body).
  • the nanostructures 54 may be formed from a different material than the substrate 52.
  • the substrate 52 may be formed from an inorganic material that is not readily imprintable/embossable, such as glass or a semiconductor material, and the nanostructures 54 may be formed from a resist material (e.g., a curable polymer) that has been applied to the substrate 52.
  • each nanostructure 54 may include a proximal end 62 and a distal end 64.
  • the proximal end 62 of each nanostructure 54 may be connected to the first major surface 56 of the substrate 52 such that the distal end 64 protrudes away from the substrate 52.
  • the z-directional spacing between the first major surface 56 of the substrate 52 and the distal end 64 of the nanostructure 54 may define the height H of the nanostructure 54.
  • the proximal end 62 of each nanostructure 54 may define the maximum width W of the nanostructure 54.
  • each nanostructure 54 may be a design consideration and may be dictated by, among other things, the operating wavelength (or wavelength range) of the anti-reflection nanostructure assembly 50. As one example, when the anti-reflection nanostructure assembly 50 is designed for 500 nm light, the height H of each
  • the nanostructure 54 may range from about 400 nm to about 600 nm. As another example, when the anti-reflection nanostructure assembly 50 is designed for visible light (about 390 nm to about 700 nm), the height H of each nanostructure 54 may range from about 350 nm to about 800 nm. As yet another example, the height H of each nanostructure 54 may range from about 100 nm to about 1500 nm.
  • the maximum width W of each nanostructure 54 may be a design consideration and may be dictated by, among other things, the operating wavelength (or wavelength range) of the anti-reflection nanostructure assembly 50. As one example, when the anti-reflection nanostructure assembly 50 is designed for 500 nm light, the maximum width W of each nanostructure 54 may range from about 400 nm to about 600 nm. As another example, when the anti-reflection nanostructure assembly 50 is designed for visible light (380 nm to 750 nm), the maximum width W of each
  • nanostructure 54 may range from about 350 nm to about 800 nm.
  • each nanostructure 54 may have an aspect ratio—the ratio of the height H to the width W— that falls within a particular range.
  • the aspect ratio of each nanostructure 54 may range from about 0.5 to about 4.
  • the aspect ratio of each nanostructure 54 may range from about 1 to about 3.
  • the aspect ratio of each nanostructure 54 may range from about 1 .5 to about 2.
  • Each nanostructure 54 may be tapered from proximate the proximal end 62 to proximate the distal end 64.
  • the taper (slope) may be gradual and substantially constant, though nanostructures 54 having a varying taper are also contemplated.
  • each nanostructure 54 may have a regular conical structure with a substantially circular cross-section in the horizontal (x-axis) plane.
  • each nanostructure 54 may have an irregular conical structure (e.g., an ellipsoidal cross-section).
  • each nanostructure 54 may have a continuous curvature.
  • each nanostructure 54 when viewed in cross-section taken in the horizontal (x-axis) plane, each nanostructure 54 may be curved (e.g., circular, ellipsoidal, etc.). In another expression, the outer surface 55 of each nanostructure 54 may be substantially free of facets. As used herein, a nanostructure 54 may be considered "substantially free of facets" if (1 ) the nanostructure 54 does not include any flat surfaces or (2) if it includes flat surfaces, but none of the flat surfaces have a characteristic length greater than 3 of the intended minimum operating wavelength of the anti-reflection nanostructure assembly.
  • the nanostructures 54 of an anti-reflection nanostructure assembly configured to operate in the visible spectrum— 380 nm to 750 nm— will be considered "substantially free of facets" if the nanostructures 54 do not include any flat surfaces having a characteristic length greater than 127 nm (one third of 380 nm).
  • facets will result in directional sensitivity to nanostructure performance. Therefore, it is believed that directional sensitivity may be reduced or eliminated by constructing the nanostructures 54 such that the outer surface 55 of each nanostructure 54 is substantially free of facets.
  • the number density of the array 60 may be a design consideration and may be dictated by, among other things, the height H of the nanostructures 54, the maximum width W of the nanostructures 54, the aspect ratio of the nanostructures 54 and the geometry of the nanostructures 54.
  • the array 60 may have a number density ranging from about 1 to about 1000 nanostructures per square micrometer of substrate 52.
  • the array 60 may have a number density ranging from about 1 to about 500 nanostructures per square micrometer of substrate 52.
  • the array 60 may have a number density ranging from about 50 to about 100 nanostructures per square micrometer of substrate 52.
  • the nanostructures 54 of the array 60 may be packed in various configurations on the first major surface 56 of the substrate 52.
  • the packing configuration may be a design consideration and may be dictated by, among other things, the geometry of the nanostructures 54.
  • the nanostructures 54 of the array 60 may be packed in a square configuration, as shown in Figs. 5A-5C.
  • the nanostructures 54 of the array 60 may be packed in a hexagonal configuration, as shown in Figs. 6A-6C.
  • the array 60 of nanostructures 54 may be a periodic array.
  • the array 60 may be a periodic array with a 20 percent position variation, as shown in Fig. 7B.
  • the array 60 may be a periodic array with a 50 percent position variation, as shown in Fig. 7C.
  • the proximal end 62 of each nanostructure 54 in the array 60 may be contiguous with the proximal ends 62 of adjacent nanostructures 54. Therefore, the proximal ends 62 of the nanostructures 54 in the array 60 may form a contiguous layer 66 over the first major surface 56 of the substrate 52.
  • the contiguous layer 66 formed by the proximal ends 62 of the nanostructures 54 may cover the first major surface 56 of the substrate 52 such that substantially none of the first major surface 56 of the substrate 52 is exposed. In one expression, the contiguous layer 66 may substantially completely cover the first major surface 56. In another expression, the contiguous layer 66 may cover the first major surface 56 such that no more than 5 percent of the first major surface 56 is exposed. In another expression, the contiguous layer 66 may cover the first major surface 56 such that no more than 3 percent of the first major surface 56 is exposed. In another expression, the contiguous layer 66 may cover the first major surface 56 such that no more than 1 percent of the first major surface 56 is exposed. In yet another expression, the contiguous layer 66 may cover the first major surface 56 such that no more than 0.5 percent of the first major surface 56 is exposed.
  • Fig. 8 provides a graphical comparison of reflectance versus wavelength for the disclosed anti-reflection nanostructure assembly (without interstitial gaps) and for a prior art anti-reflection nanostructure assembly (with interstitial gaps). Significant improvement in anti-reflection performance is observed in Fig. 8 over the entire waveband (300 nm to 1300 nm).
  • nanostructure assemblies may be applicable to any wave-based phenomena, such electromagnetic (e.g., radar) and acoustic (e.g., anechoic chambers).
  • electromagnetic e.g., radar
  • acoustic e.g., anechoic chambers
  • the disclosed anti-reflection nanostructure assembly 50 may be manufactured by etching the nanostructure array directly into the substrate, as is known in the art.
  • the nanostructure array may be formed by chemical etching, ion etching or a combination of chemical etching and ion etching.
  • the disclosed anti-reflection nanostructure assembly may be manufactured by imprinting or embossing, as is known in the art. Referring to Fig.
  • one suitable imprinting process may include an imprinting subsystem 102 that receives a film 104 (e.g., ETFE) from a supply roll 106 and outputs an anti-reflection nanostructure assembly for take-up on a take-up roll 108.
  • the imprinting subsystem 102 may include an imprinting die 1 10 and a backing die 1 12.
  • An optional heater 1 14 may be included in the imprinting subsystem 102 to heat the film 104 prior to imprinting.
  • the imprinting die 1 10 may include an imprinting surface 1 16 having a negative image of the desired nanostructure array.
  • the negative image may be formed by first constructing a master mold (not shown) having a positive image of the desired nanostructure array. Then, the master mold may be used to form the negative image on the imprinting surface 1 16 of the imprinting die 1 10.
  • the anti-reflection nanostructure assembly may be formed by pressing the film 104 between the imprinting die 1 10 and the backing die 1 12 such that the negative image on the imprinting surface 1 16 of the imprinting die 1 10 is transferred to the film 104 as a positive image. If necessary, such as when a resist material is used on the surface of the film 104, the imprinted film may be cured, such as by heating or exposing the film to ultraviolet light, to set the imprinted nanostructure array.
  • a method for reducing reflectance at an interface, such as an air-to-substrate.
  • the disclosed method 200 may smoothly vary the apparent index of refraction at the air-to-substrate interface, thereby significantly improving anti- reflection performance.
  • the method 200 may begin at Block 202 with the step of providing a substrate.
  • the substrate may be formed from an optical material, such as ETFE, glass, a semiconductor or the like.
  • the operating wavelength (or the operating wavelength range) of the substrate may be determined.
  • the operating wavelength (or the operating wavelength range) may depend on the application.
  • the operating wavelength range may include the ultraviolet to near infrared portion of the spectrum— about 350 nm to about 2,000 nm.
  • a nanostructure array may be formed on the substrate, such as by imprinting, embossing, etching or the like.
  • the nanostructure array may include nanostructures that are substantially free of facets, wherein the nanostructures include a proximal end and are tapered from the proximal end to a distal end, and wherein the proximal ends form a contiguous layer on the substrate.
  • nanostructures may be selected based on the desired operating wavelength ascertained in Block 204 or the manufacturing process selected to perform Block 206.
  • An anti-reflection nanostructure assembly comprising: an array of nanostructures, wherein each nanostructure of said array of nanostructures comprises a proximal end and a distal end, and is tapered from said proximal end to said distal end, and wherein said proximal end of each nanostructure of said array of nanostructures is contiguous with said proximal ends of adjacent nanostructures of said array of nanostructures to form a contiguous layer.
  • Clause 2 The anti-reflection nanostructure assembly of Clause 1 further comprising a substrate, wherein said contiguous layer is formed on said substrate.
  • Clause 3 The anti-reflection nanostructure assembly of Clause 2 wherein said substrate comprises an optical material.
  • Clause 4 The anti-reflection nanostructure assembly of Clause 2 wherein said substrate comprises an optical polymer.
  • Clause 5 The anti-reflection nanostructure assembly Clause 2 wherein said array of nanostructures is integral with said substrate.
  • Clause 6 The anti-reflection nanostructure assembly of Clause 2 wherein substrate and said array of nanostructures are formed from the same material.
  • Clause 7 The anti-reflection nanostructure assembly of Clause 2 wherein said substrate is formed from a first material and said array of nanostructures is formed from a second material, said second material being different than said first material.
  • each nanostructure of said array of nanostructures comprises one of a regular conical structure and an irregular conical structure.
  • Clause 9 The anti-reflection nanostructure assembly of Clause 1 wherein said taper is substantially constant from proximate said proximal end to proximate said distal end.
  • Clause 10 The anti-reflection nanostructure assembly of Clause 1 wherein distal end terminates at a pointed tip.
  • Clause 1 1 The anti-reflection nanostructure assembly of Clause 1 wherein each nanostructure of said array of nanostructures has an outer surface having a continuous curvature.
  • each nanostructure of said array of nanostructures has an outer surface, and wherein said outer surface is substantially free of facets.
  • Clause 13 The anti-reflection nanostructure assembly of Clause 2 wherein said array of nanostructures comprises about 1 to about 500 of said nanostructures per square micrometer of said substrate.
  • Clause 14 The anti-reflection nanostructure assembly of Clause 1 wherein said nanostructures of said array of nanostructures are packaged in one of a square configuration and a hexagonal configuration.
  • Clause 15 The anti-reflection nanostructure assembly of Clause 1 wherein said array of nanostructures is a periodic array.
  • Clause 16 The anti-reflection nanostructure assembly of Clause 1 wherein said array of nanostructures is a non-periodic array.
  • each nanostructure of said array of nanostructures has a height and a width, said height ranging from about 100 to about 1500 nanometers.
  • Clause 18 The anti-reflection nanostructure assembly of Clause 16 wherein a ratio of said height to said width ranges from about 1 to about 3.
  • a method for reducing reflectance at an interface comprising the steps of: forming an array of nanostructures, wherein each nanostructure of said array of nanostructures comprises a proximal end and a distal end, and is tapered from said proximal end to said distal end, and wherein said proximal end of each nanostructure of said array of nanostructures is contiguous with said proximal ends of adjacent nanostructures of said array of nanostructures to form a contiguous layer.
  • the method of Clause 19 further comprising the step of providing a substrate, wherein said array of nanostructures is positioned on said substrate.
  • each nanostructure of said array of nanostructures has a height and a width, said height ranging from about 100 to about 1500 nanometers, and wherein a ratio of said height to said width ranges from about 1 to about 3.
  • Clause 22 The method of Clause 21 further comprising the step of determining an operating wavelength or wavelength range, wherein said height and said width are selected based on said operating wavelength or wavelength range.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

La présente invention concerne un ensemble nanostructure antireflet comprenant un réseau de nanostructures (14), chaque nanostructure du réseau comportant une extrémité proximale et une extrémité distale, et étant conique de l'extrémité proximale vers l'extrémité distale, et l'extrémité proximale de chaque nanostructure du réseau étant contiguë avec les extrémités proximales de nanostructures adjacentes du réseau de sorte à former une couche contiguë.
EP14710747.8A 2013-04-30 2014-02-28 Réseau de nanostructures antireflet et procédé Pending EP2936219A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/873,320 US9207363B2 (en) 2013-04-30 2013-04-30 Anti-reflection nanostructure array and method
PCT/US2014/019514 WO2014178942A1 (fr) 2013-04-30 2014-02-28 Réseau de nanostructures antireflet et procédé

Publications (1)

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EP2936219A1 true EP2936219A1 (fr) 2015-10-28

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EP (1) EP2936219A1 (fr)
WO (1) WO2014178942A1 (fr)

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WO2015053828A2 (fr) 2013-06-15 2015-04-16 Brookhaven Science Associates, Llc Formation de surfaces antiréfléchissantes
US10189704B2 (en) 2013-06-15 2019-01-29 Brookhaven Science Associates, Llc Formation of superhydrophobic surfaces
US10290507B2 (en) 2013-06-15 2019-05-14 Brookhaven Science Associates, Llc Formation of antireflective surfaces
JP2015038579A (ja) * 2013-08-19 2015-02-26 ソニー株式会社 光学素子、光学系、撮像装置、光学機器、ならびに原盤およびその製造方法
CN108348329B (zh) * 2015-11-09 2021-07-02 Hoya株式会社 具有部分或不完整镜片的光学装置及相关联的方法
JP2019191426A (ja) * 2018-04-26 2019-10-31 フクビ化学工業株式会社 光学部材
US11487139B2 (en) 2018-11-27 2022-11-01 Applied Materials, Inc. Nanostructures for optical devices

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EP1837685A1 (fr) * 2006-03-20 2007-09-26 Nissan Motor Co., Ltd. Microstructure anti-réfléchissant, corps du moule anti-réfléchissant, et son procédé de fabrication
US20100149510A1 (en) * 2007-06-05 2010-06-17 Carl Zeiss Smt Ag Methods for producing an antireflection surface on an optical element, optical element and associated optical arrangement
EP2426520A1 (fr) * 2009-06-12 2012-03-07 Sharp Kabushiki Kaisha Film antireflet, dispositif d'affichage et élément de transmission de la lumière

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EP1837685A1 (fr) * 2006-03-20 2007-09-26 Nissan Motor Co., Ltd. Microstructure anti-réfléchissant, corps du moule anti-réfléchissant, et son procédé de fabrication
US20100149510A1 (en) * 2007-06-05 2010-06-17 Carl Zeiss Smt Ag Methods for producing an antireflection surface on an optical element, optical element and associated optical arrangement
EP2426520A1 (fr) * 2009-06-12 2012-03-07 Sharp Kabushiki Kaisha Film antireflet, dispositif d'affichage et élément de transmission de la lumière

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US9207363B2 (en) 2015-12-08
US20140320967A1 (en) 2014-10-30

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